CN105801852B - A kind of preparation method of micrometer/nanometer structure polyaniline - Google Patents
A kind of preparation method of micrometer/nanometer structure polyaniline Download PDFInfo
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- CN105801852B CN105801852B CN201610297472.7A CN201610297472A CN105801852B CN 105801852 B CN105801852 B CN 105801852B CN 201610297472 A CN201610297472 A CN 201610297472A CN 105801852 B CN105801852 B CN 105801852B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The present invention relates to a kind of preparation method of micrometer/nanometer structure polyaniline, including：Aniline monomer and monomer initiator are dissolved in lye respectively, mixed, reaction obtains aniline oligomer；Strong acid is added into aniline oligomer, adjusts pH to 0~7, then sequentially adds the doping acid solution of aniline monomer and monomer initiator, ice-water bath to 60 DEG C of 0.5~24h of reaction, washs, filter, dry, obtains micrometer/nanometer structure polyaniline.Present method avoids aniline oligomer intermediate treatment link, without template and other ancillary equipments；Whole reaction is completed in water phase, and easy to operate, controllability is strong, is adapted to large-scale production.Polyaniline prepared by the present invention can have a wide range of applications potentiality according to its conductive characteristic and architectural feature in fields such as energy storage material, sensing material, absorbing material, sorbing material and nanometer additives.
Description
Technical field
The invention belongs to the preparation field of polyaniline, more particularly to a kind of preparation method of micrometer/nanometer structure polyaniline.
Background technology
Polyaniline is a kind of highly important conducting polymer composite, there is raw material to be easy to get, is cheap, structure diversification
And advantages of environment protection.Controlled by different doping levels, polyaniline can be realized from conductor-semiconductor-insulator
Transformation.The polyaniline of nanostructured has high specific surface area, can greatly improve the contact surface of polyaniline and other materials
Product, assigns polyaniline material new characteristic.In addition, the polyaniline with different nanostructureds, such as nanofiber, nanotube, receives
Rice noodles, nanometer sheet, sea urchin shape or petal-shaped etc., can bring the new features in some structures, widen polyaniline material super
Level capacitor, electro-catalysis, gas sensing, bio-sensing, electromagnetic shielding, flexible conductive element and the field such as heavy metal ion adsorbed
Application.
At present, the preparation of the polyaniline with different nanostructureds and its pattern control are as the hot spot studied.One
As in fact, the polyaniline with different nanostructureds is mainly realized by electrochemistry and the method for chemical oxidising polymerisation.China
Patent is prepared for different nanometers with electrochemical methods such as potentiostatic method [CN1958854A], unipolar pulse methods [CN101942090B]
The polyaniline of structure, but since this method is subject to instrument and equipment, electrode area etc. to limit, it is difficult to a large amount of products are obtained, it is main to use
In laboratory research, be not suitable for large-scale production.Chemical oxidising polymerisation refers to aniline monomer and monomer initiator in acid medium
Redox reaction directly occurs to prepare polyaniline, is broadly divided into template and template-free method.Template refers in reaction solution
The soft templates such as hard template or surfactant, alkoxide such as middle addition aluminium oxide, ice crystal [CN102276831B,
CN101302292B, CN100412110C], then under the guiding of template, nanofiber, piece are obtained by chemical oxidising polymerisation
The polyaniline of the different structures such as layer, nanometer rods and nanotube.But, the higher polyaniline product of purity in order to obtain, in Hou Chu
Removing template is needed during reason, technique is very cumbersome, and can also bring destruction to the structure of polyaniline in template removal processes.
The complicated technology brought in order to avoid template and the destruction to product structure, need not add in preparation process any
The template-free method of template obtained it is widely studied, mainly including interfacial polymerization [CN100497440C, CN100480443C], outstanding
Floating polymerization [CN100526367C], emulsion polymerization [102050947B] etc..But, needed in interfacial polymerization, suspension polymerization
Organic solvent or dispersant are used, not only increases production cost, and environmental pollution can be caused；Emulsion polymerization is except above-mentioned
Shortcoming, due to the presence of emulsifying agent so that product component is complicated, it is often necessary to numerous and diverse last handling process, and also product is difficult to
Purifying, is unfavorable for industrialization large-scale production.
Except above method, the polyaniline of nanostructured, such as ultrasonic method can also be synthesized by some equipment
[CN1323199C], light irradiation method [CN100586987C], atomized drop method [CN101608018B], gravity Method
[CN102127223B], high temperature and high pressure method [CN100480302C] etc..But, these methods need to use extra instrument and equipment,
It is complicated, production cost is improved, and it is more demanding to reaction unit, it is unfavorable for the popularization and application of preparation process.
Research shows, in the aniline oligomer that can generate threadiness initial stage of polyaniline polymerization, and these oligomers are deposited
The formation and growth of polyaniline nano fiber can greatly promoted.Such as Li et al. people [Y.Li, W.He, J.Feng, and
X.L.Jing.ColloidPolym.Sci., 2012,290 (9), 817] the poly- of different supramolecular structures is prepared using two-step method
Aniline oligomer, first filters aniline oligomer reaction solution, is washed, is dried, then these oligomers are distributed to N- methyl
In the organic solvents such as pyrrolidones, then it is added drop-wise in acid solution and carries out self assembly.But, the polyaniline that prepared by this method leads to
It is often that a variety of nanostructureds coexist, it is difficult to realize the regulation and control of single even structure.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation method of micrometer/nanometer structure polyaniline, and this method uses
One kettle way mode, aniline oligomer intermediate treatment link is avoided, without template and other ancillary equipments；Entirely react in water
Completed in phase, easy to operate, controllability is strong, simple efficient, is adapted to large-scale production.
A kind of preparation method of micrometer/nanometer structure polyaniline of the present invention, including：
(1) aniline monomer and monomer initiator are dissolved in lye respectively, uniformly mixing, reaction obtains aniline oligomer；
(2) strong acid is added in the aniline oligomer obtained into step (1), pH to 0~7 is adjusted, then sequentially adds benzene
The doping acid solution of amine monomers and monomer initiator, uniformly mixing, ice-water bath is to 60 DEG C of 0.5~24h of reaction, and reaction product is through anti-
After backwashing is washed and filtered, and last low-temperature vacuum drying, obtains micrometer/nanometer structure polyaniline.
The proportioning molar ratio of aniline monomer and monomer initiator is 4 in the step (1):1~1:12.
Reaction temperature is ice-water bath to 60 DEG C in the step (1)；Reaction time is 10min~6h.
Lye is ammonia spirit in the step (1), its concentration is 0.1~3.0mol/L.
Aniline monomer concentration is 0.001~0.5mol/L after mixing in the step (1), and monomer initiator concentration is
0.001~2.0mol/L.
In step (1) neutralization procedure (2) monomer initiator be monomer initiator be the persulfuric acid such as ammonium persulfate salt,
Peroxide, the potassium permanganate such as transition metal salt, the hydrogen peroxide such as the dichromic acid such as potassium bichromate salt, iron chloride etc.；Institute
Step (1) is stated to may be the same or different with the monomer initiator in (2).
Strong acid is hydrochloric acid in the step (2), and the acidity of reaction solution is controlled by controlling the additive amount of acid；Dopant acid is
The inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, perchloric acid, fluoboric acid, oxalic acid, acetic acid, ethanedioic acid, dichloroacetic acid, acrylic acid, methyl sulphur
Acid, p-methyl benzenesulfonic acid, p-aminobenzene sulfonic acid, naphthalene sulfonic acids, salicylic acid, sulfosalicylic acid, dodecyl benzene sulfonic acid, camphorsulfonic acid etc.
At least one of organic acid.
Doping acid concentration is 0.1~6.0mol/L in the step (2)；After mixing aniline monomer concentration for 0.1~
2.0mol/L, monomer initiator concentration are 0.1~2.0mol/L, and the molar ratio of aniline monomer and monomer initiator is 4:1~1:
12。
Different pH value obtains the micrometer/nanometer structure polyaniline of different-shape in the step (2).
Polyaniline can show nanofibers, sheet, petal-shaped and the nanostructured such as spherical in the step (2), mainly
Depending on reaction system acidity and reactant concentration；According to its conductive characteristic and architectural feature, as energy storage material, sensing
Material, absorbing material, sorbing material and nanometer additive etc..
The present invention prepares the polyaniline of different nanostructureds by " one kettle way ".First synthesize benzene in alkaline solution
Amine oligomer, is then adjusted to sour environment by reaction solution, is changed to sequentially add the dopant acid of aniline monomer and monomer initiator
Solution, prepares the polyaniline of different nanostructureds.This method is avoided and cumbersome in template goes removing template mistake without template
The damage of journey and removal process to polyaniline nano structure；Woth no need to add any emulsifying agent or organic solvent, whole reaction exists
Carried out in water phase, environment-friendly and green；Also without by special instrument and equipment, simple mechanical agitation only need to be used；It is more important
Be without handling aniline oligomer, simplify synthesis technique, easy to operate, controllability is strong, is adapted to large-scale production；
And the micrometer/nanometer structure polyaniline of different performance can be prepared simply by adjusting reaction system acidity, reactant concentration.
The conductive characteristic different according to polyaniline and architectural feature, for meeting sensing material, energy storage material, sorbing material, suction
The requirement of the different field such as wave material and nanometer additive.
Beneficial effect
(1) preparation method of micrometer/nanometer structure polyaniline of the invention, first obtains aniline oligomer in alkaline solution, then
The polyaniline of different nanostructureds is prepared under differential responses system acidity, reactant concentration；Without template and add any breast
Agent or organic solvent, whole reaction carry out in water phase；Also without by special instrument and equipment；More importantly need not
Aniline oligomer is handled, simplifies synthesis technique, easy to operate, controllability is strong, is adapted to large-scale production；
(2) present invention by adjusting reaction system acidity, reactant concentration regulates and controls the self assembly behavior of aniline oligomer
With the growth course of polyaniline, and then the polyaniline of different nanostructureds is prepared；It is strong to react controllability, obtained polyaniline
With wider conductive characteristic and abundant architectural feature；
(3) present invention disclosure satisfy that sensing material, energy storage material, sorbing material, absorbing material and nanometer additive
Etc. the requirement of different field, excellent performance, is widely used.
Brief description of the drawings
Fig. 1 prepares the schematic diagram of micrometer/nanometer structure polyaniline using one kettle way；What scanning electron microscope (SEM) photograph (from left to right) provided is
The embodiment of the present invention 1,2 and 4 synthesizes micrometer/nanometer structure polyaniline；
The scanning electron microscope (SEM) photograph of polyaniline nano fiber prepared by Fig. 2 embodiment of the present invention 1；
The cyclic voltammetric of polyaniline nano fiber prepared by Fig. 3 embodiment of the present invention 1 under the sweep speed of 5mV/s is bent
Line；
The scanning electron microscope (SEM) photograph of laminar polyaniline prepared by Fig. 4 embodiment of the present invention 2；
The constant current charge-discharge curve of laminar polyaniline prepared by Fig. 5 embodiment of the present invention 2 under 2A/g current densities；
The scanning electron microscope (SEM) photograph of petal-shaped polyaniline prepared by Fig. 6 embodiment of the present invention 3；
The adsorption curve of petal-shaped polyaniline prepared by Fig. 7 embodiment of the present invention 3 under different chromium ion concentrations；
The scanning electron microscope (SEM) photograph of polyaniline spheric granules prepared by Fig. 8 embodiment of the present invention 4；
Polyaniline spheric granules prepared by Fig. 9 embodiment of the present invention 4 is under condition of different pH to the adsorption curve of chromium ion；
The scanning electron microscope (SEM) photograph of polyaniline nano fiber prepared by Figure 10 embodiment of the present invention 5；
The gas response curve of polyaniline nano fiber prepared by Figure 11 embodiment of the present invention 5 in 20ppm ammonias.
Embodiment
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Scope.
Embodiment 1
Micrometer/nanometer structure polyaniline (see Fig. 1) is prepared using one kettle way.46.565g aniline (0.5mol) is first weighed to be dissolved into
In the ammonia spirit of 800mL 3.0mol/L, 28.525g ammonium persulfates (0.125mol) are dissolved into the ammonia of 200mL 3.0mol/L
In aqueous solution, then two-phase is uniformly mixed, reacts 10min under the conditions of 60 DEG C, obtains aniline oligomer solution；Addition
400mL hydrochloric acid, strong acidity is adjusted to by reaction system, its pH value is 0；279.39g aniline (3.0mol) is weighed again to be dissolved into
In 50mL6.0mol/L camphorsulfonic acid solution, 171.15g ammonium persulfates (0.75mol) are dissolved into 50mL 6.0mol/L camphor sulphurs
In acid solution, then monomer and monomer initiator solution are added in above-mentioned aniline oligomer solution successively, in 60 DEG C of conditions
Lower reaction 0.5h；After reaction, product is by repeatedly washing, suction filtration, last vacuum dehydrating at lower temperature.Seen by scanning electron microscope
Examine, prepared polyaniline is nanofiber (see Fig. 2).Dried polyaniline powder is coated in nickel foam electricity is made
Pole, carries out cyclic voltammetry (see Fig. 3), it is 820.8F/g that specific capacitance, which is calculated, under 5mV/s sweep speeds.
Embodiment 2
First weigh 0.093g aniline (0.001mol) to be dissolved into the ammonia spirit of 800mL 3.0mol/L, 0.228g over cures
Sour ammonium (0.001mol) is dissolved into the ammonia spirit of 200mL 3.0mol/L, is then uniformly mixed two-phase, in ice-water bath bar
6h is reacted under part, obtains aniline oligomer solution；330mL hydrochloric acid is added, reaction system is adjusted to middle strong acidity, pH value is about
3.0；Weigh 13.98g aniline (0.15mol) again to be dissolved into 100mL 6.0mol/L acetic acid solutions, 486.54g iron chloride
(1.8mol) is dissolved into 70mL 6.0mol/L acetic acid solutions, and monomer and monomer initiator solution then are added to benzene successively
In amine oligomer solution, 24h is reacted under the conditions of ice-water bath；After reaction, product is last true by repeatedly washing, suction filtration
Empty low temperature drying.By scanning electron microscopic observation, prepared polyaniline is laminated structure (see Fig. 4).By dried polyaniline
Powder coating carries out charge-discharge test to electrode is made in nickel foam under 2A/g current densities (see Fig. 5), it can be seen that warp
The shape that six circulations remain to keep symmetrical triangle is crossed, illustrates that it has good stability as electrode material.
Embodiment 3
First weigh 15.832g aniline (0.17mol) to be dissolved into the ammonia spirit of 800mL 0.1mol/L, 556.060g sulphur
Sour iron (2.0mol) is dissolved into the ammonia spirit of 200mL 0.1mol/L, is then uniformly mixed two-phase, under the conditions of 60 DEG C
10min is reacted, obtains aniline oligomer solution；60mL hydrochloric acid is added, reaction system is adjusted to weak acidity, pH value is about 4.0；Again
279.39g aniline (3.0mol) is weighed to be dissolved into 100mL 0.1mol/L sulfuric acid/sulfosalisylic acid solution, 300mL30%'s
Hydrogen peroxide (3.0mol) is dissolved into 40mL 0.1mol/L sulfuric acid/sulfosalisylic acid solution, then successively by monomer and monomer
Initiator solution is added in aniline oligomer solution, and 24h is reacted under the conditions of ice-water bath；After reaction, product is through excessive
Secondary washing, suction filtration, last vacuum dehydrating at lower temperature.By scanning electron microscopic observation, prepared polyaniline is petal-like structures (see figure
6).Dried polyaniline powder is distributed in the potassium dichromate aqueous solution that concentration is 50-200mg/L, test polyaniline exists
Absorption property under different chromium ion concentrations (see Fig. 7).As can be seen that when chromium ion concentration is 150mg/L, adsorption capacity can
To reach 230mg/g.
Embodiment 4
First weigh 0.093g aniline (0.001mol) to be dissolved into the ammonia spirit of 800mL 0.1mol/L, 3.244g chlorinations
Iron (0.012mol) is dissolved into the ammonia spirit of 200mL 0.1mol/L, is then uniformly mixed two-phase, is reacted at 60 DEG C
10min, obtains aniline oligomer solution；10mL hydrochloric acid is added, reaction system is adjusted to middle strong acidity, pH value is about 6.0；Claim again
Amount 55.88g aniline (0.6mol) is dissolved into 390mL 0.1mol/L sulfuric acid solutions, and 44.13g potassium bichromates (0.15mol) are molten
Then it is molten to be added to aniline oligomer into 100mL 0.1mol/L sulfuric acid solutions by solution successively for monomer and monomer initiator solution
In liquid, 0.5h is reacted under the conditions of 60 DEG C；After reaction, product is by repeatedly washing, suction filtration, last vacuum dehydrating at lower temperature.
By scanning electron microscopic observation, prepared polyaniline is form of spherical particles (see Fig. 8).Dried polyaniline powder is distributed to
Concentration is in the potassium bichromate solution of 100mg/L, then adjusts pH value of solution, test polyaniline is under condition of different pH to chromium ion
Absorption property (see Fig. 9), it can be seen that near pH=3, maximum adsorption capacity can reach 190mg/g.
Embodiment 5
First weigh 0.093g aniline (0.001mol) to be dissolved into the ammonia spirit of 800mL 0.1mol/L, 0.228g over cures
Sour ammonium (0.001mol) is dissolved into the ammonia spirit of 200mL 0.1mol/L, is then uniformly mixed two-phase, in ice-water bath bar
6h is reacted under part, obtains aniline oligomer solution；100mL hydrochloric acid is added, reaction system is adjusted to strong acidity, pH value is about 1.0；
Weigh 13.97g aniline (0.15mol) again to be dissolved into 300mL 0.1mol/L sulfosalisylic acid solutions, 40.55g potassium peroxydisulfates
(0.15mol) is dissolved into 100mL 0.1mol/L sulfosalisylic acid solutions, then successively by monomer and monomer initiator solution
It is added in aniline oligomer solution, 24h is reacted under the conditions of ice-water bath；After reaction, product is by repeatedly washing, pumping
Filter, last vacuum dehydrating at lower temperature.By scanning electron microscopic observation, prepared polyaniline is nanofiber (see Figure 10).By drying
Polyaniline powder afterwards is distributed in ethanol, and a certain amount of product is then added dropwise to sensing element, is surveyed under 20ppm ammonia concns
Try its gas response curve (see Figure 11).
Claims (9)
1. a kind of preparation method of micrometer/nanometer structure polyaniline, including：
(1) aniline monomer and monomer initiator are dissolved in lye respectively, mixed, reaction obtains aniline oligomer；
(2) strong acid is added in the aniline oligomer obtained into step (1), pH to 0~7 is adjusted, then sequentially adds aniline list
The doping acid solution of body and monomer initiator, ice-water bath to 60 DEG C of 0.5~24h of reaction, washs, filters, dry, obtains nano junction
Structure polyaniline.
A kind of 2. preparation method of micrometer/nanometer structure polyaniline according to claim 1, it is characterised in that the step (1)
The molar ratio of middle aniline monomer and monomer initiator is 4:1~1:12.
A kind of 3. preparation method of micrometer/nanometer structure polyaniline according to claim 1, it is characterised in that the step (1)
Middle reaction temperature is ice-water bath to 60 DEG C；Reaction time is 10min~6h.
A kind of 4. preparation method of micrometer/nanometer structure polyaniline according to claim 1, it is characterised in that the step (1)
Middle lye is ammonia spirit, and concentration is 0.1~3.0mol/L.
A kind of 5. preparation method of micrometer/nanometer structure polyaniline according to claim 1, it is characterised in that the step (1)
Aniline monomer concentration is 0.001~0.5mol/L after middle mixing, and monomer initiator concentration is 0.001~2.0mol/L.
A kind of 6. preparation method of micrometer/nanometer structure polyaniline according to claim 1, it is characterised in that the step (1)
Monomer initiator is persulfate, bichromate, transition metal salt, peroxide or potassium permanganate in neutralization procedure (2)；Its
In, persulfate is ammonium persulfate；Bichromate is potassium bichromate；Transition metal salt is iron chloride；Peroxide is peroxidating
Hydrogen.
A kind of 7. preparation method of micrometer/nanometer structure polyaniline according to claim 1, it is characterised in that the step (2)
Middle strong acid is hydrochloric acid；Dopant acid is sulfuric acid, nitric acid, phosphoric acid, perchloric acid, fluoboric acid, acetic acid, ethanedioic acid, dichloroacetic acid, propylene
Acid, pyrovinic acid, p-methyl benzenesulfonic acid, p-aminobenzene sulfonic acid, naphthalene sulfonic acids, salicylic acid, sulfosalicylic acid, dodecyl benzene sulfonic acid,
At least one of camphorsulfonic acid.
A kind of 8. preparation method of micrometer/nanometer structure polyaniline according to claim 1, it is characterised in that the step (2)
Middle doping acid concentration is 0.1~6.0mol/L；Aniline monomer concentration is 0.1~2.0mol/L after mixing, monomer initiator concentration
For 0.1~2.0mol/L；The molar ratio of aniline monomer and monomer initiator is 4:1~1:12.
A kind of 9. preparation method of micrometer/nanometer structure polyaniline according to claim 1, it is characterised in that the step (2)
Middle nanostructured is threadiness, sheet, petal-shaped or spherical nanostructure.
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| CN111850815A (en) * | 2020-07-22 | 2020-10-30 | 陕西科技大学 | Polyaniline/nano cellulose fiber composite conductive film and preparation method thereof |
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| CN110358344B (en) * | 2018-04-11 | 2021-04-20 | 成功大学 | Method for producing anticorrosive paint |
| CN110868098B (en) * | 2019-11-28 | 2020-10-30 | 中国科学院兰州化学物理研究所 | Self-powered ammonia sensing friction nano generator and preparation method and application thereof |
| CN111644161B (en) * | 2020-06-12 | 2022-04-05 | 中国科学院合肥物质科学研究院 | Modified fiber ball loaded polyaniline composite material and preparation method and application thereof |
| CN113174043A (en) * | 2021-05-19 | 2021-07-27 | 东华大学 | Preparation method of polyaniline material with three-dimensional hierarchical micro-nano structure |
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